The chemical compounds present on the surface of CdTe have been investigated after different surface preparations and correlated with the properties of junctions formed by Cr on the CdTe. X-ray photoelectron spectroscopy (XPS) analysis indicates that four different surface compositions result from five different treatments. Cleaving leaves a stoichiometric surface whereas oxidation in air leads to the formation of TeO2. Bromine-in-methanol etch leaves a Te-enriched surface and chromate etch leaves a surface containing both TeO2 and excess Te. Hydrogen heat treatment of an etched CdTe surface restores a stoichiometric cleavedlike surface from that disrupted by the etching process. Effects on the properties of subsequently formed junctions are evidenced by a decrease in the diode saturation current from 2×10−5 for a bromine-etched surface to 2×10−8 A/cm2 for a cleaved surface.